CN1680009A - Preparation of sodium polyimide filtering membranes for concentrated extracted liquid of antibionic solvent - Google Patents
Preparation of sodium polyimide filtering membranes for concentrated extracted liquid of antibionic solvent Download PDFInfo
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- CN1680009A CN1680009A CN 200510042378 CN200510042378A CN1680009A CN 1680009 A CN1680009 A CN 1680009A CN 200510042378 CN200510042378 CN 200510042378 CN 200510042378 A CN200510042378 A CN 200510042378A CN 1680009 A CN1680009 A CN 1680009A
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Abstract
A nano-class filtering polyimide membrane for concentrating the antibiotic extracting solvent is prepared through preparing the filming liquid from the polyimide imidated partially, filming by phase transfer method, and heat post treating for imidating and cross-linking. It can be used for the antibiotic-solvent separation system.
Description
Technical field:
The present invention relates to a kind of preparation method who is used for the polyimide filtering membranes of concentrated extracting with antibiotic dissolved medium liquid.Prepared NF membrane belongs to organic high molecular layer.Specifically, be to adopt phase inversion to prepare the polyimides polymeric membrane, casting solution is formed and control inversion of phases film forming condition by regulating, and prepared a series of NF membrane can be fit to separate different antibiotic/solvent separation system.
Background technology:
In typical antibiotics production technology, the antibiotic stoste that fermentation method is produced needs through solvent extraction, just finally obtains finished product through washing, acid adjustment degree, reversed phase extraction, filtration, a series of complicated technologies such as concentrated again.In this process, organic solvent, alkali, acid solution use repeatedly, and consumption is big, and technological process is long, and the antibiotic yield is low.Solvent adopts the way of distillation to reclaim, and power consumption is big, is the main power consumption section in the antibiotics production technology.The use of big liquid measure solvent has also produced a series of side effect simultaneously, for example: make product yield low, increased the load of subsequent technique, water-washing process produces a large amount of antibiotic waste waters that contains, increase wastewater treatment capacity and intractability, be used to regulate the soda acid consumption increase of acid-base value in the reversed phase extraction process, the solvent loss amount is big or the like.Therefore, development of new antibiotic refinement technique, the shortcoming that overcomes traditional handicraft becomes problem demanding prompt solution.
Membrane separation technique has no phase transformation, low energy consumption, high efficiency separation characteristic because of it, has caused increasing attention in the last few years in pharmaceutical industry.Adopt membrane technology to improve the shortcoming that antibiotics production technology can overcome existing antibiotics production technology.Existing antibiotic extraction process is carried out improved mode have two kinds: the one, adopt the hydrophilic film that the antibiotic fermentation filtrate without extraction is concentrated, remove and anhydrate and inorganic salts, concentrate is used solvent extraction again; The 2nd, after using the solvent extraction antibiotic, extract is handled with film, concentrates antibiotic.The former technology can reduce the consumption of extractant, unit capacity is increased, but, still contain the pollutant of higher concentration owing to the zymotic fluid of handling through plate compression, comprise impurity such as low molecular weight protein, inorganic salts, these impurity can produce serious pollution to separation membrane surface.By contrast, adopt film to concentrate the antibiotic extract, have following advantage:
1. save the investment heat energy required of solvent evaporation equipment, reduced the recovery cost of extractant, also improve operating environment simultaneously, avoid the harm of solvent vapo(u)r the workman with evaporation;
2. the no phase transformation of membrane separation technique operation, and separative efficiency height do not destroy the structure of product, and in addition, because solvent extraction liquid is after concentrated, liquor capacity reduces, and antibiotic concentration improves greatly, thereby has improved the reversed phase extraction yield.Like this, two aspects integrate and make final antibiotic product yield be largely increased.
3. through the film after separating, the extract quantitative change is little, so institute's water requirement reduces in the extract washing operation, not only can reach the water saving purpose, can also reduce quantity of wastewater effluent.
4. under the identical situation of output, install required processing liquid measure and reduce, this provides the foundation for the dilatation of device.
5. can reduce the consumption of solvent.In the traditional handicraft, the consumption of solvent is generally hundred million potency units of 5～6kg/10, uses the inventive method, and the solvent that diffusion barrier is passed in infiltration directly refluxes, and this part consumption can be reduced to minimum.
6. equipment and technological process are simpler, and membrane module can carry out modularized design, are easy to amplify and build, simultaneously, because the handled feed liquid of diffusion barrier is a solvent extraction liquid, impurity content wherein is less, and film is vulnerable to pollution not, therefore, device is long the duration of runs, is easy to management and maintenance.
Research that existing patent documentation is reported and application mainly concentrate on the former technology, the influence that lagged behind by anti-solvent NF membrane exploitation, the rare research of latter process.At present there is not specialty to be used to separate the patent report of antibiotic/anti-organic solvent film preparation of solvent system as yet.
Polyimides is a base polymer that contains imide group on the main chain, generally is with quaternary carboxylic acid dianhydride and binary primary amine polycondensation and get, anti-solvent, low temperature resistant, heat-resisting, intensity is big, is the membrane material that performance is very good, can be used for preparing anti-solvent system.Mobil company in 1998 and Grace company adopt commodity Matrimid by name
TMThe aromatic polyimide of 5218 complete imidizate has been developed the organic solvent-resistant film, is successfully applied to the removal process of 300,000 tons of lubricating oil ketone-benzol dewaxing device butanone, toluene, for a frontier has been opened up in the development and application that film separates.Phase inversion is effective process means of preparation organic high molecular layer, and many product films all are by this explained hereafter.Phase inversion prepares the polymeric membrane needs and polymeric film material and additive is dissolved in is mixed with casting solution in the solvent earlier, therefore requires polymeric film material to have solubility.But because monomer structure, intermolecular cross-linking reaction takes place in most of polyamic acids easily when imidizate, and the gained polyimides is insoluble material, is difficult to prepare required film by phase inversion.At present, the material system film of employing part imidizate is not also arranged to overcome the bibliographical information of the poorly soluble problem of polyimides.
Summary of the invention:
The objective of the invention is to provide a kind of preparation method who is used for the polyimide filtering membranes of concentrated extracting with antibiotic dissolved medium liquid.
The objective of the invention is to be achieved through the following technical solutions.
The first step: with polyimides, water-soluble polymer additive and polar aprotic solvent by mass ratio (13～17): (2.3～5.5): the proportional quantities of (50～55) places container, electromagnetic agitation makes it dissolving evenly under the room temperature, remove by filter insoluble impurities, filtrate is left standstill the degassing, makes basic casting solution.Said polyimides is synthetic by aromatic diamine and aromatic tetracarboxylic acid's dianhydride, and its degree of imidisation is 50%～95%.The water-soluble polymer additive can be polyvinyl alcohol, polyethylene glycol and polyvinylpyrrolidone.Polar aprotic solvent is dimethylacetylamide, N-methyl pyrrolidone and methyl-sulfoxide isopolarity non-protonic solvent, or the mixture of above-mentioned solvent and acetone, oxolane volatile solvent.
Second step: basic casting solution moulding, can be made into two kinds of films of flat sheet membrane and hollow-fibre membrane, the preparation method of flat sheet membrane is: under 10～40 ℃, casting solution is coated at the bottom of the porous on the supporter, after 10～150 seconds volatilization time of control, freezing film obtains polyimide filtering membranes in the immersion coagulating bath; The preparation method of hollow-fibre membrane is: under 10～40 ℃, casting solution is spun into the hollow fiber nanofiltration membrane type with the doughnut spinning-drawing machine, obtains polyimides after the immersion coagulating bath is solidified, spinning core liquid is identical with coagulating bath.
The 3rd step: the film that solidifies after the typing obtains can be used for the finished product polyimide filtering membranes that extracting with antibiotic dissolved medium liquid concentrates after a series of exchange of solvent and heat cross-linking post processing, detailed process is only with film rinsing 1～24 hour in coagulating bath, film experience exchange of solvent and dry after, crosslinked 1～30 minute, the environment temperature of heat cross-linking post processing was 100～250 ℃.
The specific embodiment:
Below in conjunction with embodiment in detail the present invention is described in detail.
Following examples will help to understand the present invention, but be not limited to the present invention.
Embodiment 1, the preparation method of the dull and stereotyped NF membrane of polyimides: weighing is dried to the polyimides 15g of constant weight under 50 ℃, electromagnetic agitation makes it to be dissolved in the mixed solvent of 30mL N-methyl pyrrolidone and 24mL acetone under the room temperature, add 3.5g polyvinyl alcohol additive, dissolving evenly, after filtering with 300 order stainless (steel) wires, it is standby that filtrate is left standstill the degassing 24 hours.Under dustless, 30 ℃, relative humidity 50% condition, above-mentioned gained casting solution is coated on glass plate or the porous bottom, film forming thickness is controlled at about 50um, the 60 seconds volatilization time of control, immerses film forming in the water coagulating bath then.
The post-processing approach of film: rinsing is after 24 hours in coagulating bath with film, and film soaked 24 hours at ethanol, isopropyl alcohol successively, after drying, placed under 150 ℃ of environment heat treatment 10 minutes.
Membrane separating property: with 10150 potency units/milliliter spiramvcin-butyl acetate solution is feed liquid test membrane separating property, under the room temperature, feed liquid flow rate 15.0L/h, operating pressure are 3.0MPa, embodiment 1 prepared film is 99.5% to the rejection of spiramvcin, and permeation flux reaches 35L/m
2H.
Embodiment 2, the preparation method of polyimides hollow fiber nanofiltration membrane: get dried soluble polyimide 150g, electromagnetic agitation makes it to be dissolved in the mixed solvent of 300mL N-methyl pyrrolidone and 240mL acetone under the room temperature, add the 30g polyvinyl alcohol, dissolving evenly, after filtering with 300 order stainless (steel) wires, it is standby that filtrate is left standstill the degassing 24 hours.Under 25 ℃ of normal temperature, casting solution is spun into hollow-fibre membrane with the doughnut spinning-drawing machine, coagulating bath and core liquid are water, and control spinneret and coagulating bath distance are 25cm, and spinning speed is 2.5 meter per seconds, and the core flow velocity is 2.8m/s.
The post-processing approach of film: with rinsing in the obtained hollow-fibre membrane coagulating bath 24 hours, then in ethanol, isopropyl alcohol, n-hexane, soak after 24 hours successively, place under 150 ℃ of environment heat treatment 10 minutes.
Membrane separating property: with 10150 potency units/ml erythromycin-butyl acetate solution is feed liquid test membrane separating property, under the room temperature, feed liquid flow rate 15.0L/h, operating pressure are 2.0MPa, embodiment 1 prepared film is 97.0% to the rejection of spiramvcin, and permeation flux reaches 20L/m
2H.
It is that 50%～95% polyimides is a membrane material that the present invention adopts the imidizate degree, after treating forming film with phase transformation method, carry out complete imidizate and intermolecular cross-linking by hot post processing again, improve nanofiltration film strength and pore structure stability, overcome the bad shortcoming of polyimides dissolubility of complete imidizate, make inversion of phases legal system film become feasible, and this method is simple, prepared serial NF membrane is applicable to different antibiotic/solvent separation system, be specially adapted to separate the organic solvent solution of recovery molecular weight at 300～1200 daltonian antibiotic and medicine intermediate, with the isolated molecule amount less than 1200 dalton, molecular weight differs the above organic mixture of 250 dalton, between 95.0%～99.9%, the solvent permeation flux satisfies the commercial Application requirement to the antibiotic rejection.And the present invention is applied to polyimide film material in antibiotic/organic solvent separation system first.
Claims (2)
1. preparation method who is used for concentrating the polyimide filtering membranes of extracting with antibiotic dissolved medium liquid is characterized in that realizing according to the following steps:
The first step: with polyimides, water-soluble polymer additive and polar aprotic solvent by mass ratio (13～17): (2.3～5.5): the proportional quantities of (50～55) places container, electromagnetic agitation makes it dissolving evenly under the room temperature, remove by filter insoluble impurities, filtrate is left standstill the degassing, makes basic casting solution; Said polyimides is synthetic by aromatic diamine and aromatic tetracarboxylic acid's dianhydride, and its degree of imidisation is 50%～95%; The water-soluble polymer additive can be polyvinyl alcohol, polyethylene glycol and polyvinylpyrrolidone; Polar aprotic solvent is dimethylacetylamide, N-methyl pyrrolidone and methyl-sulfoxide isopolarity non-protonic solvent, or the mixture of above-mentioned solvent and acetone, oxolane volatile solvent.
Second step: basic casting solution moulding, can be made into two kinds of films of flat sheet membrane and hollow-fibre membrane, the preparation method of flat sheet membrane is: under 10～40 ℃, casting solution is coated at the bottom of the porous on the supporter, after 10～150 seconds volatilization time of control, freezing film obtains polyimide filtering membranes in the immersion coagulating bath; The preparation method of hollow-fibre membrane is: under 10～40 ℃, casting solution is spun into type with the doughnut spinning-drawing machine, obtains the polyimides hollow fiber nanofiltration membrane after the immersion coagulating bath is solidified, spinning core liquid is identical with coagulating bath.
The 3rd step: the film that solidifies after the typing obtains can be used for the finished product polyimide filtering membranes that extracting with antibiotic dissolved medium liquid concentrates after a series of exchange of solvent and heat cross-linking post processing, detailed process is only with film rinsing 1～24 hour in coagulating bath, film experience exchange of solvent and dry after, crosslinked at ambient temperature 1～30 minute.
2. preparation method according to claim 1, the environment temperature that it is characterized in that said heat cross-linking post processing is 100～250 ℃.
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| CN1314478C CN1314478C (en) | 2007-05-09 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102527264A (en) * | 2012-02-22 | 2012-07-04 | 苏州乐华新材料有限公司 | Method for preparing polyimide hollow fiber |
| CN104797327A (en) * | 2012-11-20 | 2015-07-22 | 环球油品公司 | Cross-linked polyimide membranes for separations |
| CN105566907A (en) * | 2016-03-22 | 2016-05-11 | 天津工业大学 | Polyimide nanofiltration membrane prepared on basis of synergic imidization and method thereof |
| CN107803119A (en) * | 2017-11-03 | 2018-03-16 | 宁夏大学 | A kind of preparation method of composite film and the method using residual tetracycline in its removal pharmacy waste water |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2101137B (en) * | 1981-04-14 | 1984-09-26 | Ube Industries | Producing porous aromatic imide polymer membranes |
| CN1068974A (en) * | 1991-07-31 | 1993-02-17 | 中国科学院长春应用化学研究所 | The preparation of asymmetric polyimide gas separation membrane |
| US5635067A (en) * | 1995-03-14 | 1997-06-03 | Praxair Technology, Inc. | Fluid separation membranes prepared from blends of polyimide polymers |
| JPH10330482A (en) * | 1997-04-04 | 1998-12-15 | Nitto Denko Corp | Polyimide and its production, and gas separable membrane by using the same and its production |
| CN1099310C (en) * | 1998-04-16 | 2003-01-22 | 中国科学院大连化学物理研究所 | Preparation of asymmetrical hollow polyimide fibre membrane |
| CN1377725A (en) * | 2001-03-29 | 2002-11-06 | 中国科学院大连化学物理研究所 | Macroporous polymer filtering membrane and its prepn. |
-
2005
- 2005-01-20 CN CNB2005100423789A patent/CN1314478C/en active Active
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102527264A (en) * | 2012-02-22 | 2012-07-04 | 苏州乐华新材料有限公司 | Method for preparing polyimide hollow fiber |
| CN104797327A (en) * | 2012-11-20 | 2015-07-22 | 环球油品公司 | Cross-linked polyimide membranes for separations |
| CN105566907A (en) * | 2016-03-22 | 2016-05-11 | 天津工业大学 | Polyimide nanofiltration membrane prepared on basis of synergic imidization and method thereof |
| CN107803119A (en) * | 2017-11-03 | 2018-03-16 | 宁夏大学 | A kind of preparation method of composite film and the method using residual tetracycline in its removal pharmacy waste water |
| CN107803119B (en) * | 2017-11-03 | 2021-01-05 | 宁夏大学 | Preparation method of composite film and method for removing residual tetracycline in pharmaceutical wastewater by using composite film |
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| CN1314478C (en) | 2007-05-09 |
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Owner name: DALIAN OAK MEMBRANE TECHNOLOGY ENGINEERING CO., LT Free format text: FORMER OWNER: PETROLEUM UNIVERSITY (EASTERN CHINA) Effective date: 20100622 |
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Free format text: CORRECT: ADDRESS; FROM: 257061 NO.271, BEIER ROAD, DONGYING DISTRICT, DONGYING CITY, SHANDONG PROVINCE TO: 116035 NO.537, HOUGE STREET, GANJINGZI DISTRICT, DALIAN CITY, LIAONING PROVINCE |
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Effective date of registration: 20100622 Address after: 116035 Dalian, Liaoning, Ganjingzi District, after the leather street, No. 537 Patentee after: Dalian Ouke Membrane Technology Engineering Co., Ltd. Address before: 257061 North Dongying Road, Dongying, Shandong, No. two, No. 271 Patentee before: University of Petroleum (East China) |